Solution-phase photochemistry of a [FeFe]hydrogenase model compound: Evidence of photoinduced isomerisation
- Department of Physics, University of Strathclyde, SUPA, Glasgow G4 0NG (United Kingdom)
- Energy Materials Laboratory, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ (United Kingdom)
- WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL (United Kingdom)
The solution-phase photochemistry of the [FeFe] hydrogenase subsite model ({mu}-S(CH{sub 2}){sub 3}S)Fe{sub 2}(CO){sub 4}(PMe{sub 3}){sub 2} has been studied using ultrafast time-resolved infrared spectroscopy supported by density functional theory calculations. In three different solvents, n-heptane, methanol, and acetonitrile, relaxation of the tricarbonyl intermediate formed by UV photolysis of a carbonyl ligand leads to geminate recombination with a bias towards a thermodynamically less stable isomeric form, suggesting that facile interconversion of the ligand groups at the Fe center is possible in the unsaturated species. In a polar or hydrogen bonding solvent, this process competes with solvent substitution leading to the formation of stable solvent adduct species. The data provide further insight into the effect of incorporating non-carbonyl ligands on the dynamics and photochemistry of hydrogenase-derived biomimetic compounds.
- OSTI ID:
- 22047165
- Journal Information:
- Journal of Chemical Physics, Vol. 136, Issue 4; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
CO-Bridged H-Cluster Intermediates in the Catalytic Mechanism of [FeFe]-Hydrogenase CaI
Cell-free H-cluster Synthesis and [FeFe] Hydrogenase Activation: All Five CO and CN– Ligands Derive from Tyrosine